Understanding

Rheology of Thermosets

revised by A.J. Franck, TA Instruments

Rheology of Thermosets

Rheological Testing of
Thermosetting Polymers
General Considerations
Thermoset Polymer Uses
Thermoset polymers form the
matrix in filled plastics and fiberreinforced composites used in a
diversity of products. These range
from consumer items and auto
body panels to advanced composites for printed circuit boards
(PCBs), aerspace structural
compo-nents such as the Space
Shuttle payload bay door and jet
engine cowls and ducts, and expensive, high-performance sports
equipment. Also, thermosets are
used extensively as adhe-sives,
molding compounds, and surface
coatings, including protective solder masks for PCBs.
Thermosets versus Thermoplastics and Elastomers
Thermoset polymers are distinguished from elastomers and
thermoplastic polymers in several
ways.
Thermoplastics are processed in
the molten state, their final shape
and internal structure established
by cooling, and they can be softened and reshaped by reapplication of heat and pressure. Also,
their polymer chains, whether linear or branched, remain di-screte
after molding. Thermoset polymers usually go through three
stages. In the A-stage, sometimes called a resole, the resin is
still soluble and fusible. In the Bstage, thermosets are nearly insoluble, but are still thermoplastic. They can, however, spend only
a rela-tively short time in the molten state because the temperatures that promote flow also cause
the material to crosslink. The
crosslinking reaction is accomplished in the final stages of polymerization the C-stage during molding of the product under
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the controlled influence of heat

and pressure over time. Thus,
thermosets build their final structure during processing, forming a
three-dimensional internal structural network of highly crosslinked
polymer chains. And the final
product is insoluble and not thermally reformable.
Elastomers share characteristics of thermoplastics and
thermosets. Elastomers begin
as thermoplastic polymers with
discrete chains that later develop
a network of covalent crosslinks.
However, elastomers are distinguished from thermosets by the
fact that the crosslink network is
formed in a separate post-polymerization step called vulcanization.
Another factor distinguish-ing the
three classes of polymers is the
glass transition temperature T g
the temperature at which polymers reversibly transmute between rubbery and glassy states.
For elastomers, the glass transition tempe-ature is below ambient temperatures; for thermoplastics and thermosets, it is substantially above ambiant.
Studying the Crosslinking
Reaction
The formation of a thermoset
crosslinked network is shown
schematically in figure 1.
Understanding of this pro-cess
has been advanced substantially
by use of rheological analysis
measurements of resin viscosity,
shear modulus, and damping.
More sensitive than even Fourier
transform infrared spectroscopy
for measuring extent of cure,
rheological testing has become
a vital supplement to DSC, chromatography, and wet chemical
analysis in thermoset polymer
re-search and develop-ment. The
reasons for this reside in the na-

3
ture of the processes involved
and the rheological changes inherent in these.

Thermoset Processing
Multistage Processing
Quite commonly, thermosetting
resins are processed in two or
more stages, as, for example, are
those used in the production of
fiber reinforced laminates.
First, a laminating varnish is produced from resin monomer, curing agent, other functional additives, and a suitable solvent.
Then this varnish is applied to a
reinforcing fabric made of glass
fiber or other high modulus
fibers, the solvent is removed,
and the resin is partially reacted
to form a prepreg. At this point,
the B-stage, the prepreg is a partially soluble, low-melting thermoplastic solid composed of
unreacted monomer, adduct (the
re-action product of a one-to-one
ratio of resin and curing agent),
and higher molecular weight
oligomers. Some resins, particu-

Rheology of Thermosets
larly epoxies, must be protected
from moisture and refrigerated to
forestall advancement, that is,
conti-nuation of the reaction.
To fabricate a product, a multilayer
sandwich of prepreg is prepared,
placed in a press or autoclave,
and heated to cure. This
processing step must accomplish several things: wet the
fibers thoroughly with resin, consolidate the laminate to the desired thickness, remove excess
resin, exhaust trapped air, moisture, and solvent to avoid porosity, and advance the cross-linking reaction to the desir-ed level.
As the temperature is raised, the
prepreg melts and its viscosity
drops precipitously, then levels off
and again climbs. This viscosity
behavior is the consequence of
the intervention of a competing
circumstance: The rising temperature triggers further reaction
among monomer, curing agent,
and oligomers increasing the prepregs viscosity. Because the
reactants are multi-functional,
crosslinks form among the polymer chains quickly in all directions.
Suddenly the system gels and
flow ceases. At this point, the
matrix is solid and the thickness
and shape of the composite are
fixed. Additional heating is needed, however, for the matrix to
form the balance of ist potential
crosslinks and to develop, for the
most part, ist ultimate level of stiffness. To accomplish this, an additional out-of-mold post-cure step
is generally used.
Single-stage Processing

Figure 1: Schematic representation of structural development

during thermoset curing: (A) unreacted monomers; (B) formation
of small branched molecules; (C) the gel point: a path of covalent
bonds exists across the sample; (D) the cured, crosslinked polymer
with some unreacted groups and reactants.
A.Franck

Thermosets are also pro-cessed

in a single-stage method called
reaction injection molding (RIM).
In use on a major scale since late
in the seventies, RIM has become
popular for a variety of automotive
and recreational applications.
In some respects, RIM resembles thermoplastic injection
molding (TIM). The key difference,
however, is that RIM uses polym10/04 V1

Rheology of Thermosets

erization in the mold rather than

cooling to form a solid polymer.
Other reaction molding processes
also use polymerization to solidify
the molded piece; however, in
thermoset injection molding, for
example, reactants are heated to
around 200 C to activate the reaction. In RIM, the reactants are
combined at a relatively lower temperature (about 40C) because the
reaction is activated by impingement mixing, not external heat.
In the RIM process, complex
plastic parts are quickly produced
directly from low viscosity reactants. Two or more liquids are
impin-gement mixed at low temperatures and pres-sures as they
enter the mold. Solid polymer
forms by phase separation of segmented block copolymers (but
structural buildup by crosslinking
occurs with some urethane systems) and parts can be removed
from the mold in under a minute.

Process Rheology
Thermoset structural development
is accompanied by enormous
rheological changes: The resin
changes from a low-melting thermoplastic solid to a low viscosity
liquid, to a gel, and then to a stiff
solid.

Log o, *,Goo

Thus, the properties are vitally

important to successful process-

liquid

solid

*
G

tc

Reaction time

Figure 2: Measurement of the viscosity of a curing epoxy resin in

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ing. In structural laminates, resin

flow influences porosity, cured
part dimensional uniformity, and
process economics. In multilayer
printed wiring boards, resin flow
properties also influence uniformity of etched circuit encapsulation, copper-to-epoxy adhesion, and final press thickness.
Therefore, at each stage of the
pro-cess, the rheological state
should be known to employ these
materials effectively and economically.
The rheology of thermosetting resins can be studied using both
steady shear and dynamic oscillatory tests (sometimes referred
to as dynamic mechanical analysis (DMA) or dynamic mechanical rheological testing ( DMRT).
How steady shear, dynamic, and
transient tests are run is described in a later section.
Steady shear measurements can
characterize only the initial portion of a thermosets viscosity
range. Near the gel point the
steady shear viscosity increases rapidly and becomes
unmeasurable. Eventually the
stiffening sample fractures or
tears.
In contrast, dynamic oscillatory
measurements of the resins viscosity can be made as the reaction proceeds through the gel point
and beyond until the resin
becomes a stiff solid. This is possible because the measurements
can be made at a strain amplitude low enough to prevent disruption of the gel structure as it is
being formed. Steady shear viscosity data are compared to dynamic viscosity data for a curing
epoxy resin in figure 2.
Being able to measure the viscosity throughout the thermoset curing reaction is an important capability. Still, it provides only a
partial picture of the phenomenon
taking place. Because the material is viscoelastic, elasticity data
are needed to complete the characterization. These are obtained
in a dynamic test concurrent with

Rheology of Thermosets

measurement of the viscosity.

Figure 3 shows the storage (G)
and loss (G) moduli and complex viscosity * measured during an epoxy molding compound
cure. Besides providing essential mini-mum viscosity data, the
cross-over point of the two modulus curves gives an estimate of
the time at which the resin begins to gel.
But this is only an ap-proximate
gel point. The problem is this: As
the transient gel network structure is forming, stress relaxation
is also taking place. So, unless
measurements on the gelling system are made extremely rapidly,
the exact time of gelation will be
obscured by changes due to
stress relaxation.
Recent work by H.H. Winter1
shows that the cross-over point
of the storage and loss modulus
curves is not the true gel point.
Rather, the instant of gelation is
when the critical gel exhibits
power law stress relaxation and
tan momentarily becomes independent of frequency. This point
can be identified by making several frequency sweeps simulta-

10

10

10

10

10

Moduli G', G'' [Pa]

10

G'
G''
*

approx. gel point

10

10

Minimum viscosity

10

80

100

120

140

160

Temperature T [C]

Figure 3: Measurement of the minimum viscosity and

approximate gel point for a curing epoxy molding compound

Complex viscosity * [Pas]

Temperature ramp 5 C/min

neously, measuring tan d in the

time scale of the developing gel.
Figure 4 shows dynamic oscillatory measurements of tan d made
simultane-ously at three frequencies on a crosslinking polydimethylsiloxane (PDMS) resin.
Because tan is independent of
frequency at the gel point, the
three curves pass through a single point and unambiguously define the instant of gelation. Such
measurements are readily made
using a Rheometric rheometer
equipped with the MultiWave
mode, described in detail in a later
section.

Product Performance
To derive optimum perform-ance
from a thermoset resin, both
undercure and overcure must be
avoided. An undercured matrix
may exhibit creep and tend to
build up heat upon vibrat-ing; an
overcured matrix may experience room temperature performance problems because internal
stresses build up in the glassy
polymer as it cools, and stress
cracks develop later.
A parameter known as the glass
transition temperature Tg, often
measured during DSC and TGA,
has been used as an indicator of
the extent of thermoset resin cure.
For example, compared to a fully
cured control sample of known
good performance, a lower glass
transition temperature indicates
undercure.
But this does not necessarily
mean that a higher Tg indicates
overcure: The difference between
complete cure and overcure cannot be detected by measuring T g.
A higher glass transition temperature may result form exposure
later to temperatures above those
of cure or postcure. The glass
transition temperature can be
lower if the prepreg were cut and

1
Fourier Transfom Mechanical Spectroscopy of Viscoelastic Materials with Transient Structure
E.E. Holly, S.K. Venkataraman, F. Chambon and H.H. Winter, Journal of Non-Newtonian Fluid Mechanics, 27(1988)17-26

A.Franck

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Rheology of Thermosets

frequencies
1 rad/s
4 rad/s
16 rad/s

tan

gel point

10

30

32

34

36

38

40

time t [min]

Figure 4: The precise gel point of a curing resin is identified by

the intersection of tan curves generated in several
simultaneous frequency sweeps
laid up in a high relative humidity. (This can be verified by
retesting after drying the sample,
since the effect is reportedly reversible.) And formulation errors
can shift the glass transition temperature up or down.
To understand the inadequacy of
Tg alone as a performance gauge,
what Tg is must be understood.
The glass transition is a temperature-induced morphological
change in a polymer between a
brittle, glassy state and a viscous,
rubbery state. The glass transition temperature Tg is the temperature at which this transition
occurs.
Because the material ex-periences
a substantial change in rigidity in
a short span of temperatures,
the glass transition is a key factor in deciding the use-fulness
of a polymer. So, merely knowing the temperature at which it
occurs (all that DSC and TGA
provide) is not enough. The
modulus must be measured as
a function of temperature as well.
This is accomplished most effectively using dynamic mechanical rheological testing .
In the course of measuring the
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moduli (G, G) and damping

behavior (tan ) of a polymer at a
chosen oscillatory frequency over
a sufficiently wide range of temperature, the effect of the glass
transition can be clearly observed. The glass transition is
detected as a sudden and considerable (several decades)
change in the elastic modulus and
an attendant peak in the tan
curve.
Besides being a more accurate
method for measuring T g, DMRT
reveals much about the material
before and after the glass transition because DMRT also measures the rubbery plateau modulus. This is important because, at
high thermoset cure levels, the
rubbery plateau modulus is more
sensitive than is Tg itself for detecting, for example, small differences in a thermoset polymer cure
level.
Also called the a transition, the
glass transition is associated with
crank-shaft motion of major chain
segments. Other transitions, designated as b, g, etc. in order of
descending temperature of occurrence, arise from vibrations and
rotations. Material toughness and
impact resistance correlate with
the magnitude of tan at the secondary (, ) peaks.
For many materials, as the dynamic oscillatory frequency is
increased, transitions occur at
higher temperatures. Also, some
transitions shift different amounts,
depending on their degree of frequency dependence. This helps
locate some transitions in
multiphase resin systems (such
as those modified by addition of
elastomers or thermoplastics) if
one component is more frequency-dependent than another.
Shifts in the glass transition temperature and the b peak can indicate the effect of compounding or
process changes on product performance. In general, the temperature of the secondary transition shifts more than does the

7
glass transition temperature as
frequency is changed.
How dynamic mechanical testing
can be employed to study the critical aspects of thermoset rheology during resin curing and solid
state finished product performance is described in the following
sections.

Sample Selection and

Preparation
If the immediate application involves use of the neat resin, then
tests should be run on material in
that form. If, however, prepregs are
used, then tests should be made
on the staged resin mechanically
extracted form the prepreg, or directly on die-cut samples of laminates (for example, a three-ply
laminate of prepreg stacked with
the middle and top ply oriented at
45 and 90 with respect to the
fiber orientation of the bottom ply).
The die size is dictated by the
diameter of the parallel plates to
be used for the dynamic mechanical tests. Disposable plates,
should be used for tests that
cause the resin to cure since the
resin can adhere strongly to the
plates. The sample should be
pressed (under vacuum, if possible) to reduce ist bulk and hold
the plies together. To avoid slippage, the test should be begun
at a temperature at which the
resin is tacky.
Powdered resin samples should
be pulverized, dried, and pressed
in a mold, forming a wafer of a
size matching the test plates diameter.

Generating Viscosity
Profiles
Developing the proper cure level
is perhaps the most critical step
for a thermoset polymer. And both
under-curing and overcuring must
be avoided.
The most effective and economical way to do this is to design a
thermoset cure cycle derived
A.Franck

Rheology of Thermosets
from measurements of the curing resins dynamic viscosity profile as a function of temperature
and time.
Rheometers are designed to facilitate making these measurements: A time/cure mode allows
test temperatures to be advanced
(ramped) at rates of 1 to 5C per
minute in eight separately controlled heat zones. Each zone can
be programmed for a ramp rate,
final temperature, total time,
measure time, and percent strain.
Thus, almost any cure cycle can
be conveniently simulated. And
rheometers are equipped with a
MultiWave mode that provides the
most precise measurement of the
gel point available by measur-ng
tan d in several simultaneous frequency sweeps.
From a series of measure-ments
at different temperature ramping
rates (generally 1 to 5C per
minute), the storage (G) and loss
(G) moduli and the complex viscosity * are derived, and the following key information is obtained:

Initial viscosity

Minimum viscosity

Gel point

Optimum heating rate

Initial Viscosity
The initial viscosity, the first point
of the viscosity profile, indicates
the onset of matrix melting, and
is not influenced by heating rate.
It is a useful indicator of degree of
resin advancement for quality control.
Minimum Viscosity
The minimum viscosity represents
the time period and temperature
range over which resistance to
flow is lowest. Knowing this and
the time needed to reach the minimum viscosity is critical in various processes: In laminate production, the resin viscosity must
10/04 V1

Rheology of Thermosets
be low enough to wet the embedded fibers uniformly, but not so
low as to cause excessive bleeding at the laminate edges. And in
the encapsulation of integrated circuits by transfer molding, the viscosity must be low enough to
avoid damaging the fragile wires
that connect the circuits to the
frame. The time interval during
which the viscosity is at or near
ist minimum value constitutes the
processing window.

Complex viscosity * [Pa s]

10

Heating rate
o
3 C/min
o
2 C/min
o
1 C/min

10

Gel Point
1

10

1000

2000

3000

4000

5000

6000

time t [min]

Figure 5: Measurement of the viscosity profile of a curing

thermoset resin as a function of heat-up rate

Pressure is needed during lamination to squeeze the plies together, and timing is critical: Substantial pressure must not be applied until after the minimum viscosity has been reached, else the
resin will bleed excessively at the
edges; but it must be applied before the gel point to assure adequate compaction.

Isothermal cure at different temperatures

6

10

10

Pressure is used also to control

outgassing of volatile by-products
generated in some thermoset
polymer reactions such as those
involved in the manufacture of
polyimides.

TGDDM + DDS 100/30

10

viscosity * [Pas]

10

10

173 C
165 C
152 C
143 C
129 C

Excessive pressure must be

avoided during the lamination of
circuit boards that include an oxide-prepreg interfacial treatment
since sme oxides are fragile and
can be crushed, causing delamination.

10

10

-1

10

-2

10

-3

10

10

10

time t [s]

Figure 6: Isothermal scans at various temperatures are used to help

decide on the time interval and temperature at which to impose
isothermal holds during a thermoset resin production cure cycle
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The gel point is the temperature

or time at which the first set of
covalent bonds connects across
the sample (the onset of a threedimensional network) and the
molecular weight becomes infinitely large. The gel point is important in determining the time
and temperature at which pressure should be applied.

Optimum Heating Rate

The heating rate must be optimized
because it affects the time
needed to reach the minimum viscosity, and the time and temperature intervals over which the mini-

Rheology of Thermosets

10

Temperature
Pressure
Viscosity

180
160

Temperature T [C]

120
100

10

80
60

Viscosity * [Pas]

10

140

20
0

10
0

Time t [hours]

Figure 7: A thermoset resin production cure cycle in which

hydraulic pressure is induced in the resin to reduce gas
bubble nucleation in the cured matrix

The time at or near the minimum

viscosity is a key factor in controlling overall flow and avoiding
problems such as bulk porosity.
A second hold near the gel point
is sometimes used to eli-minate
surface porosity. Typical isothermal scans are shown in figure 6.

Temperature ramp 2 C/min

Test frequency 10 rad/s

G', G'' [Pa]

Using the Viscosity

Profile

100000

w/o Zn-stearate
w Zn-stearate
1

time t [min]

Figure 8: The addition of zinc stearate lowers resin

viscosity at the injection mold barrel temperature without
affecting the cure time
A.Franck

Isothermal Scans
Once the minimum visco-sity and
gel point have been determined,
a series of isothermal scans
should be run at temperature intervals beginning with the minimum viscosity temperature and
continuing up to the gel point temperature in intervals of about 10C.
These scans can be made quickly
on the ARES since it can can
record one data point a second.
This information will help in deciding the time and temperature
at which to impose isothermal
holds during the process. An isothermal hold at minimum viscosity extends the time the resin will
remain near the minimum viscosity and determines the dimensions of the processing window.

10

40

mum viscosity extends. Too fast

a heating rate can create unwanted temperature differentials
within the part, irregular curing
throughout the piece, and possible porosity problems. Figure 5
shows the effect of heat-up rate
on the viscosity profile.

A dynamic mechanical viscosity

profile offers unparalleled utility in
every phase of thermoset polymer
technology, including research,
product development; process
development and control; and
quality control. Some examples
follow.
Research
Dynamic mechanical testing is
employed extensively in thermoset composites research to provide needed material properties for
10/04 V1

10

Rheology of Thermosets
finite element and finite difference
analyses. And dynamic viscosity
profiles provide vital data for studies of cure reaction kinetics, process modeling using expert systems, and advanced curing concepts such as gas diffusion control.

200
180

Temperature T [C]

160
140
120
100

Diffusion control reduces gas bubble nucleation in the curing matrix by inducing hydraulic pressure in the resin during the gas
volatilization stage of the cure
cycle. Figure 7 shows a typical
matrix resin cure cycle incorporating diffusion control, superimposed on the viscosity profile.

80
60
40

50

100

150

200

Time t [min]

Product Development
Figure 9: A graphite-epoxy production cure cycle

Viscosity profiles are used to

great advantage in ther-moset
product development to evaluate,
for example,

Temperature T [C]

300
280
260
240
220

Press Molding Cycle

200
180
0

50

100

150

200

250

300

350

400

450

Temperature T [C]

Time t [min]

fiber types, finishes, and

weaves

materials from alternati

ve suppliers; and

functional additives

Process Development
and Control

300

Developing Production Cure

Cycles

250

A dynamic mechanical viscosity

profile provides the rheological
data needed to construct a production cure cycle. Figure 9
shows a typical cure cycle developed for a graphite/epoxy laminate.

Post cure cycle

200

50

100

150

200

250

300

350

400

450

Time t [min]

Figure 10: The cure and post-cure cycles for a polyimide resin
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new or different resin

formulations

Figure 8 shows how the viscosity

profile during cure has been used
to evaluate, at a typical screw
barrel temperature, the beneficial
effect of adding 1% zinc stearate
to a phenolic injection molding
compound. The zinc stearate lowered the viscosity considerably at
the barrel temperature without affecting cure time.

320

-50

500

550

Developing Post-Cure Cycles

11

Rheology of Thermosets

10

Temperature
No advancement
advanced
further advanced

10

600

10

400

10

B-stage advanced

Viscosity * [Pas]

Tempertaure T [C]

800

Quality Control

200

10

10

The cure step is the most critical

element in ther-moset processing. Accordingly, maintenance of
strict quality control standards on
the incoming materials, the
prepreg especially, is important.
Two areas of major concern are
degree of resin advancement and
the effects of moisture.

20

40

60

80

100

120

140

160

In many cases, especially with

bismaleimides and polyimides, a
post-cure step is used. This involves heating the laminate for an
extended time outside the mold
to increase the crosslink density
and raise the glass transition temperature of the matrix, thereby
improving functional properties. A
typical post-cure cycle in a circulating air oven for a polyimide resin
composite used for a jet engine
component is shown in figure 10.

180

Time t [min]

Figure 11: B-stage resin advancement alters the viscosity

profile of a curing thermoset resin

Prepreg Advancement

1000
1000

Test frequency 10 rad/s

0% rel. humdity
75% rel. humidity

800

600

10

400

0.1

200

0.01
0

20

40

60

80

100

120

140

160

180

time t [min]

Figure 12: Viscosity profiles of a dry epoxy resin and the

same resin after extended storage in a high humidity
A.Franck

200

Temperature T [C]

viscosity * [Pas]

100

Prepregs are partially re-acted by

the supplier to differentdegrees to
develop particular properties (stiffness, tack, drape) needed for a
given application. The degree of
reaction advancement in the Bstaged prepreg is controlled
mainly by stoichiometry and storage conditions, including duration,
humidity, and teperature. Ideally,
prepregs should be stored only a
short time, and then in a cold, dry
environment. Any lapses in supplier quality control or improper
storage may cause the reaction
to advance, changing the materials response in a standard cure
cycle.
Tests on prepreg samples immediately prior to use can quickly
identify advancement level differences so that adjustments can be
made to the cure cycle. Figure
11 shows viscosity profiles of an
epoxy resin at three different levels of minimum viscosity and the
reaction rate (reflected in the slope
of the viscosity curve during the
isothermal hold), and the sooner
gelation occurs.

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12

Rheology of Thermosets
Moisture Effects

0.07
0.06

0.04

Modulus G'
tan

tan

Modulus G' [Pa]

0.05

0.03
0.02
0.01

1E10
-200

-100

100

200

300

400

Temperature T [C]

Figure 13: Temperature sweep on a cured epoxy-graphite

composite. The glass transition is manifested in a sudden and
considerable decrease in the storage modulus with an
attendant peak in the tan curve

Evaluating Product
Performance
Key factors in thermoset polymer
product performance are the
cured resins modulus and glass
transition temperature. The dynamic moduli (G, G or E, E)
are measured directly on solid
samples with or without fiber reinforcements at a selected frequency as a function of temperature. And from these measurements tan is automatically
calculated. The glass transition is
detected as a sudden and considerable decrease in the storage
modulus and an attendant peak
in the tan curve. The symbol T g
denotes the temperature at which
this transition occurs.

1E10
1

1E9

Tan

G' [Pa]

0.1

1E8
0.01

second run high to low

first run low to high
1E7
-150

-100

-50

50

100

150

Temperature T [C]

Figure 14: Different values of the glass transition

temperature are obtained if the transition is approached
while the sample is being cooled compared to when the
sample is being heated
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Moisture adsorbed during improper storage of a prepreg can

create quality problems in thermoset processing by changing reaction kinetics and there-by changing the viscosity profile of the
prepreg. Also, trapped moisture
can cause matrix porosity. By
testing before use, moisture-related cure problems can be
avoided, or at least minimized.
The effects of moisture are often
reversible, so the material may be
salvaged by drying before curing.
Figure 12 shows the viscosity profiles of a dry epoxy resin and the
same resin after extended storage in a high humidity.

200

Figure 13 shows the tan and

storage modulus curves, the
glass transition and secondary
transition of an epoxy-graphite
sample measured in bending on
the Solids Analyzer. The glass
transition temperature is not a
constant, so care must be taken
during its measure-ment to avoid
generating misleading data. For
example, two tests made at different heating rates can produce
different values of the glass transition temperature. The slower the
measurement, the lower is the
glass transition temperature.

13

Rheology of Thermosets
Also, for valid comparisons to be
made, the glass transition temperature must be approached from
the same direction to avoid hysteresis during the test. So, data
from test samples should be compared to data from tests made
under the same conditions (including oscillation frequency) on
good-performing control samples.

100

1E11

Frequencz 1Hz
10

1E9

tan

Storage Modulus G' [Pa]

1E10

0.1
1E8

Azelaic acid & BOMA

BOMA
DDM
BTDA

1E7

-150

-100

-50

50

100

150

200

250

300

0.01

1E-3
350

Figure 16 shows the effects of

various curing agents on the glass
transition temperature of an epoxy
resin.

Temperature T [C]

Figure 15: Temperature sweeps are an effective means for

detecting the effects of different curing agents on the
viscoelastic properties of thermoset resins

The data in figures 14 through 16

were obtained in bending and torsion. Figure 15 shows the glass
transition temperature as a function of cure level measured in tension following the procedure outlined in ASTM D5026.

1
9

Curing Temperature
93 C
135 C
350 C
10

10

0.1

tan

Modulus G' [Pa]

10

Figure 15 shows the effect on the

glass transition temperature of
going from a low to high temperature and then repeating the test
as the sample cools, using a
cured and a cured plus postcured
sample of PMR-15 polymimide.

0.01
-200

-150

-100

-50

50

100

150

200

250

300

Temperature T [ C]

Figure 16: The cure level of a thermoset polymer as a

function of cure temperature measured in torsion. Tests can
also be run in compression or bending.

A.Franck

10/04 V1

Keywords: thermopsets, processing, elasticity, cure, viscosity, performance, gel point, vitrification,
glass transition

copyright TA Instruments 2004